PL200931B1 - Herbicidal emulsifiable concentrates - Google Patents

Abstract

The invention relates to a non-aqueous herbicide preparation in the form of an emulsifiable concentrate, containing: (a) 25-150 g/liter of at least one fluorinated herbicide compound of formula I, in which R 1 , R 3 , R 2 , min have meanings given in the description; (b) 400-900 g/liter of one or more alkyl phenoxyalkanoate herbicides; (c) 10-100 g/liter of at least one non-ionic surfactant; (d) 10-100 g/liter of at least one benzenesulfonate; (e) 50-600 g/liter of one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, methylated vegetable oils and water-miscible polar aprotic organic solvents; and (f) optionally up to 5 g/liter of antifoaming agent. The invention also relates to a method of combating undesirable vegetation in the place of occurrence. PL PL PL PL

Description

The invention relates to a non-aqueous, emulsifiable herbicidal formulation and a method for controlling undesirable vegetation.

Formulations in the form of emulsifiable concentrate (EC) are the preferred liquid delivery systems for the active ingredient for use in agriculture. Typically, known EC formulations contain the active ingredient, one or more surfactants which act as emulsifiers upon dilution of the EC with water, and a water-immiscible solvent. Typical solvents for use in EC formulations are aliphatic or aromatic hydrocarbons such as, for example, xylene, Shellsol A or Solvesso 200. These solvents are sparingly soluble in water and are able to dissolve a wide variety of active ingredients.

Due to the presence of a solvent, many EC formulation pesticides have advantages such as a higher degree of systemicity and a higher overall activity compared to the same pesticides in the form of powder for suspensions (WP), water dispersible granules (WG) or suspension concentrate (SC ).

Such concentrates are easy to store and transport, and various auxiliaries can be added to them to increase the effectiveness of the formulation. However, a good EC formulation should meet the requirement that when diluted with water, a stable emulsion is formed which does not separate on standing. Moreover, upon dilution with water, no crystallization of the active ingredient from the EC should take place. In addition, the EC formulation must be physicochemically stable over a longer period of storage and at a storage temperature that varies over a wide range.

WO 98/48624 suggests that the improvement in the stability of an EC emulsion containing a small amount of water-insoluble fluorinated active ingredients used in agriculture and possibly containing an agricultural active ingredient serving as an extender is achieved by using a relatively large amount of water-insoluble C6 -C18-alkylpyrrolidone. However, C6-C18-allkylpyrrolidones are highly corrosive compounds and are too expensive to be used in many commonly used herbicidal products.

Furthermore, WO 98/48024 preferably uses nonylphenol ethoxylate as the anionic surfactant. These surfactants can be harmful to the environment due to their ability to form toxic metabolites and their use is not preferred because they are suspected to be oestrogenic.

There was therefore a need to provide new herbicidal emulsifiable concentrates, in particular a stable and effective EC formulation containing a low amount of at least one fluorinated herbicidal compound and a high amount of one or more alkyl herbicidal phenoxyacetate diluent without the drawbacks of known EC formulations, as well as a method of controlling undesirable weeds by contacting the plants with a herbicidally effective amount of an EC formulation after dilution with water, and further providing selective herbicides obtained by emulsifying the new EC formulations in water.

The invention relates to a non-aqueous herbicidal formulation in the form of an emulsifiable concentrate containing herbicidally active compounds for plant protection, characterized in that it comprises:

(a) 25-150 g / liter of at least one fluorinated herbicidal compound of general formula I

in which 1 3

R ¹ and R ³ independently represent fluoro or fluoroalkyl, ₂

R ² is hydrogen or optionally substituted alkyl or alkoxy; amines independently represent an integer of 1-2;

(b) 400-900 g / liter of one or more herbicidal alkyl phenoxyalkanoates, (c) 10-100 g / liter of at least one non-ionic surfactant,

(D) 10-100 g / liter of at least one benzenesulfonate, (e) 50-600 g / liter of one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, methylated vegetable oils and water-miscible polar oils aprotic organic solvents, and (f) optionally up to 5 g / L of antifoam.

Preferably, the formulation according to the invention contains as herbicidal fluorinated compound (a)

N- (4-fluorophenyl) -2- (3-a, α, α-trifluoromethylphenoxy) -6-pyridine carboxamide.

Preferably the formulation according to the invention comprises an alkyl phenoxyacetate of the general formula II as herbicidal alkyl phenoxyalkanoate (b)

wherein

R ⁴ independently represents halogen or C1-C6 alkyl,

R ⁵ and R ⁶ independently represent C 1 -C 6 alkyl,

R ⁷ is hydrogen or methyl and t is an integer of 1-3.

Preferably the preparation according to the invention as alkyl phenoxyacetate (b) comprises a compound selected from the group consisting of 2-ethylhexyl (4-chloro-2-methylphenoxy) acetate, 2-ethylhexyl (2,4-dichlorophenoxy) acetate and 2- (4-chloro-2) 2-ethylhexyl-methylphenoxy) propionate and mixtures thereof.

Preferably, the formulation according to the invention comprises ethoxylated castor oil as the nonionic surfactant (c).

Preferably, the formulation according to the invention comprises calcium alkylbenzenesulfonate as (d).

Preferably, the formulation according to the invention comprises:

(a) 30-125 g / liter of at least one fluorinated herbicidal compound of formula I;

(b) 700-875 g / L of one or more herbicidal alkyl phenoxyalkanoates of formula II;

(c) 20-75 g / L of at least one nonionic surfactant;

(d) 20-75 g / L of at least one sodium or calcium alkylbenzene sulfonate;

(e) 50 - 200 g / l one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, (C ₈ - ₁₂₎ -karboksylany methyl, N-methylpyrrolidone, γ-butyrolactone and isopropyl lactate; and (f) optionally up to 2 g / L of at least one antifoam agent selected from the group consisting of polydimethylsiloxanes and perfluoroalkylphosphonic / perfluoroalkylphosphinic acids.

The invention also relates to a method for controlling undesirable vegetation at a locus, which comprises emulsifying the formulation as defined above with water and treating the site with the resulting dilute aqueous formulation.

As used herein with reference to the new EC formulations, the term "herbicidal compound" means a synthetic compound which is capable of controlling undesirable weeds in crops; and "a fluorinated herbicidal compound is a synthetic compound substituted with at least one fluorine atom having the ability to control undesirable weeds in crops.

Useful fluorinated herbicidal compounds are those which are solid at room temperature and are substantially insoluble in water but soluble in an organic solvent.

Preferred fluorinated herbicides (a) are compounds selected from the group consisting of: acifluorfen, ethylcarfentrazone, propargylclodinafop, diflufenican, dithiopyr, ethylethoxyphene, isopropylflamprop-M, methylflamprop-M, flazasulfuron, fluazifop, flufuchloramidin, flufuchloramide, flufuchloramid (BAY). flumioxazine, fluometuron, fluoroglycophen, flupoxam, fluridone, fluroxypyr, flurprimidol, flurtamone, methylflutiacet, fomesafen, haloxyfop, isoxaflutole, lactophen, norflurazone, oxyfluorfen, picolinfen, flupoxam, propachlorinopentraz, and trifluralinopentraz.

Most of these herbicidal compounds are described in "The Pesticide Manual, 11th Edition, The British Crop Protection Council and The Royal Society of Chemistry, 1997, (hereinafter abbreviated as" Pesticide Manual ").

PL 200 931 B1

Particularly preferred herbicidal compounds (a) are the picolinamides disclosed in EP-A-0447004, and especially those of formula I1

wherein R ¹ and R ² are as defined for formula I.

A particularly preferred compound for use in the present invention is N- (4-fluorophenyl) -2- (3-a, α, α-trifluoromethylphenoxy) -6-pyridinecarboxamide, also known as picolinafen.

The herbicidal compounds can be e.g. compounds which show high herbicidal activity over a wide concentration range and / or in low doses, and can be used in agriculture, in particular for the selective control of undesirable vegetation such as Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Lamium purpureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retroflexus, and they can be used pre- and post-emergence, especially in certain crops such as maize and rice.

Suitable herbicidal alkyl phenoxyalkanoates (b) are those which are liquid at room temperature and substantially insoluble in water but soluble in an organic solvent.

Preferred alkyl phenoxyalkanoates are esters of 2-phenoxyacetic or 2-phenoxypropionic acid containing a straight or branched C2-C12 alkyl group, in particular a branched C4-C10 alkyl group. 2-ethyl hexyl esters are most preferred.

The most preferred compounds are 2-ethylhexyl 4-chloro-2-methylphenoxyacetate [also known as MCPA-2EH], (2-ethylhexyl 2,4-dichlorophenoxyacetate [also known as 2,4-D-2EH] and 2- ( 2-ethylhexyl 4-chloro-2-methylphenoxy) propionate [also known as mecoprop-2EH] or mixtures thereof.

Mixtures of the aforementioned herbicides or mixtures of herbicides with other active ingredients, such as fungicides, insecticides, acaricides and nematicides, are possible.

Suitable nonionic surfactants (c) are preferably polyglycol ether derivatives of alcohols and aliphatic and saturated or unsaturated fatty acids containing 3-20 glycol ether groups and 8-20 carbon atoms in the (aliphatic) hydrocarbon group. Other suitable nonionic surfactants are ethylene oxide and propylene oxide polyadducts containing 20-250 ethylene glycol ether, ethylene diamine poly (propylene glycol) and alkyl poly (propylene glycol) groups having 1-10 carbon atoms in the alkyl group. These materials typically contain 1-5 ethylene glycol units per propylene glycol unit. Examples of nonionic surfactants are polyethylene glycol castor oil ethers, polyethylene oxide polyadducts with propylene oxide, tributylphenoxypolyethoxyethanol and ethoxylated tristyrylphenol.

Ethoxylated oils such as castor oil or low erucic ethoxylated rapeseed oil containing at least 25, preferably 27-37 ethoxy mers, such as Sunaptol® CA350 (ethoxylated castor oil with about 35 ethoxy units) from Uniqema (formerly ICI Surfactants), Mergital ® EL33 (ethoxylated castor oil containing approx. 33 ethoxy units) from Henkel KGaA, Eumulgin® C03373 (ethoxylated low erucic rapeseed oil containing approx. 30 ethoxy units) from Henkel KGaA and Ukanil® 2507 (ethoxylated low erucic rapeseed oil containing approx. 32 mers of ethoxy) .

Another group of preferred nonionic surfactants (c) are alcohol alkoxylates which contain alkoxy units with 2 carbon atoms and therefore are mixed ethoxylates or with 2 and 3 carbon atoms and are therefore mixed ethoxylates / propoxylates. In a preferred alkoxylate of the aliphatic alcohol, the alkoxylate chain may be at least 5 alkoxy units, suitably 5-25 alkoxy units, preferably 5-15 and especially 5-11, preferably 5-11. The alcohol moiety is typically derived from a C9-C18 aliphatic alcohol. The preferred alcohols are usually 50 wt.% Alcohols. % straight chain and 50 wt. branched.

PL 200 931 B1

Particularly preferred surfactants are ethoxylated alcohols

Synperonic® from Uniqema, in particular Synperonic® 91-6.

In addition, preferred alcohol alkoxylates are monobranched alcohol ethoxylates such as Atplus® MBA 11-7 (C11 ethoxylated branched alcohol containing 7 ethoxy units) from Uniqema or Genapol® X-60 (ethoxylated alcohol containing 6 ethoxy units) from Clariant.

Suitable alkyl benzene sulphonates (d) are, for example, sodium, calcium or triethylammonium alkylbenzene sulphonates. The most preferred alkylbenzene sulphonates (d) are sodium, calcium or triethylammonium dodecylbenzene sulphonate, in particular Rhodacal® 70 / B (70% calcium dodecylbenzene sulphonate in n-butanol), Rhodacal® 60 / BE (60% calcium dodecylbenzene sulphonate in 2-ethylhexanol) and Rhodacal® 2283 (70% ammonium dodecylbenzenesulfonate) all from Rhodia GmbH (formerly Rhone-Poulenc), Phenylsulfonat CA 100 (40% calcium dodecylbenzenesulfonate), Genopol X-060 and Salvesso 200 from Clariant GmbH (formerly Hoechst AG) or Nansa® EVM 70 / 2E ( 57% linear dodecylbenzenesulfonate in 2-ethylhexanol) from Albright & Wilson.

The surfactants (c) and (d) provide good emulsifying properties and do not contain alkylphenol ethoxylates such as Synperonic® NP9 and / or anionic derivatives thereof, e.g. alkylaryl phosphate ethoxylates such as Rhodofac® RE 610. Alkylphenol ethoxylates and their derivatives may harm the environment due to their ability to form toxic metabolites and because they are suspected to be oestrogenic.

Suitable solvents (e) are non-polar, water-immiscible solvents or polar aprotic water-miscible organic solvents. The non-polar solvents are selected from the group consisting of aliphatic or aromatic hydrocarbons and esters of vegetable oils or mixtures thereof.

Aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene, mineral oil or kerosene or substituted naphthalenes, mixtures of mono- and polyalkylated aromatics are e.g. commercially available under the trademarks Solvesso®, Shellsol®, Petrol Spezial® and Exxsol®.

The vegetable oil esters which are used as non-polar, water-immiscible solvents according to the invention are usually alkyl esters obtained from medium-chain fatty acids by esterification with alkanols or by transesterification of suitable vegetable oils, preferably in the presence of a lipase. Preferred fatty acids of these vegetable oils contain 5-20, especially 6-15 carbon atoms. In a preferred embodiment of the invention, the vegetable oil methyl ester used is a methyl ester of caprylic / capric or capric acid with a chain length distribution of about 10 mer.

Particularly preferred vegetable oil methyl esters are Witconol® 1095 and Witconol® 2309, commercially available from Witco Corporation, Houston, USA.

Water-miscible polar aprotic organic solvents are preferred compounds which exhibit a dielectric constant of 2.5 or higher at 25 ° C, especially 2.7-4.0 at 25 ° C.

Cyclic amides and lactones are particularly preferred, such as, for example, N-methylpyrrolidone, N-cyclohexylpyrrolidone and γ-butyrolactone, with γ-butyrolactone and N-methylpyrrolidone or mixtures thereof being most preferred.

Furthermore, water-miscible polar aprotic solvents selected from the group consisting of alkyl lactates, in particular isopropyl lactate such as Plurasolv® IPL, available from Plurac, alkyl carbonates, polyethylene glycols, polyethylene glycol alkyl ethers, polypropylene glycols and glycol alkyl ethers are further preferred. polypropylene, isopropyl lactate or mixtures thereof being most preferred.

Suitable antifoams (f) are siloxane derivatives or perfluoroalkylphosphonic acids / perfluoroalkylphosphinic acids, in particular polydimethylsiloxanes such as Rhodorsil® 416 or Rhodosil® 454 from Rhodia or mixtures containing perfluoro- (C6-C18) -alkylphosphonic (C6-C18) alkylphosphonic acids ) -alkylphosphine such as Fluowet® PL80, Fluowet® PP from Clariant.

Various preferred and extremely advantageous formulations according to the invention can be used from among the formulations given below:

(a) 30-125 g / liter, especially 40-110 g / liter, of at least one fluorinated herbicidal compound of formula I, especially a compound of formula I1, most preferably picolinafen;

(b) 700-875 g / liter, especially 750-850 g / liter, of one or more herbicidal alkyl phenoxyalkanoates of formula II, most preferably 2,4-D-2EH, MCPA-2EH or mecoprop-2EH;

(C) 20-75 g / liter, in particular 40-70 g / liter, of at least one nonionic surfactant, especially at least one ethoxylated castor oil;

(d) 20-75 g / liter, in particular 40-70 g / liter, of at least one sodium or calcium alkylbenzene sulfonate;

(e) 50-200 g / liter, especially 60-150 g / liter, of one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, methyl (C8-C12) carboxylates,

N-methylpyrrolidone, γ-butyrotactone and isopropyl lactate; and (f) optionally up to 2 g / L of at least one antifoam agent selected from the group consisting of polydimethylsiloxanes and perfluoroalkylphosphonic / perfluoroalkylphosphinic acids.

The emulsifiable concentrates described above are prepared by mixing all ingredients in a dissolver apparatus.

The compositions obtained by emulsifying the formulation according to the invention in water can be used as pesticides for controlling pests at the site of occurrence by treating the site with these agents.

As consumer products, the pesticidal EC formulations are preferably present in a concentrated form, whereas the end user generally uses diluted compositions. Such compositions may be diluted down to a concentration of up to 0.001% active ingredient (s.c.). Usually doses in the range of about 0.01-10 kg a.c. / ha are used.

Such compositions may also contain other adjuvants such as chemical stabilizers, viscosity regulating agents, thickeners, tackifiers, fertilizers, or other active pesticidal ingredients to provide additional effects.

The formulations according to the invention show high physicochemical stability, despite the high concentration of herbicidally active substances (a) and (b). Emulsions obtained from these EC formulations upon dilution in water are surprisingly stable, although do not contain any additional C6-C18-alkylpyrrolidones.

The following examples illustrate the invention.

Manufacturing examples

Registered trademarks and other markings apply to the following products:

Ingredient Composition Manufacturer AgsolEx® 1 N-methylpyrrolidone AND SP AgsolEx® BLO γ-Butyrolactone AND SP Altox® 4855B Blend of calcium alkylarylsulfonate and nonionic surfactant in an aromatic solvent Uniqema Exxsol®D110 A mixture of aromatic hydrocarbons Exxon Chemicals Fluowet® PL80 Mixture of 80% perfluorinated phosphinic / phosphoric acids and 20% water Clariant Plurasolv® IPL Isopropyl lactate Plurac Rhodacal® 70 / B 70% Calcium Dodecylbenzenesulfonate Rhodia Rhodacal® 60 / BE 60% Calcium Dodecylbenzene sulfonate Rhodia Rhodorsil® 454 A mixture of polydimethylsiloxanes and silica Rhodia Solvesso 200 A mixture of aromatic hydrocarbons Exxon Chemicals Ukanil® 2507 Castor oil, ethoxylated Uniqema Witconol® 1095 Technical methyl decanoate Witco Corp.

PL 200 931 B1

Examples 1-3

EC preparations were produced containing:

Ingredient Function Concentration (g / l) Example 1 2 3 Picolinafen Active substance (s) 50 50 50 MCPA 2-EH Active substance (s) 780 780 780 Altox 4855 B Emulsifying system (c) + (d) 100 100 100 Fluowet PL 80 Defoamer (f) 0.5 0.5 0.5 Solvesso 200 Solvent (s) up to 1 liter - - Purasolv IPL Solvent (s) - up to 1 liter - Exxsol D 110 Solvent (s) - - up to 1 liter

Foaming ability

The foaming capacity was assessed by the MT47 CIPAC method and is shown in Table 1 below

T a b e l a I Foaming capacity

Test Example 1 Example 2 Example 3 Persistent foam (2% in CIPAC Standard Water C) after 10 s 7.5 ml 10 ml 2.5 ml after 1 min 0 ml 0 ml 0 ml after 3 min 0 ml 0 ml 0 ml after 12 min 0 ml 0 ml 0 ml

The properties of EP formulations were assessed according to the following CIPAC procedures.

Characteristics of the emulsion (CIPAC MT 36)

The appropriate EC formulation (5 mL) is mixed with water (342 ppm hardness) to form 100 mL of an aqueous emulsion. The stability of the emulsion is judged on the oil or cream that separates when the emulsion is left intact for 24 hours at 30 ° C. The ability to re-emulsify after a period of 24 hours is also determined.

B) Durability at low temperature (CIPAC MT 39)

A sample of the respective EC formulation is kept for 1 hour at 0 ° C and then the volume of any isolated solid or oily substance is recorded. The sample is stored for 7 days and then left undisturbed at ambient temperature for 3 hours. Then the sample is centrifuged and the presence of the separated solid and its volume are recorded.

The diluted spray formulations appeared to be homogeneous emulsions that were completely stable for at least 2 hours at 30 ° C (CIPAC MT 36 method). No solids precipitated from the preparations when stored for 7 days at 0 ° C (CIPAC MT 39 method).

P r x l a d y 4-6

EC preparations were produced containing:

Ingredient Function Concentration (g / l) Example 4 5 6 1 2 3 4 5 Picolinafen Active substance (s) 50 50 50 MCPA 2-EH Active substance (s) 780 780 780 Ukanil 2507 Non-ionic surfactant (c) 60 - 50

PL 200 931 B1 cont. table

1 2 3 4 5 Rhodacal 60 / BE Anionic center surfactant (d) 60 - - Rhodacal 70 / B Anionic center surfactant (d) - - Atlox 4855 B Emulsifying system (c) + (d) - 100 - Rhodorsil 454 Defoamer (f) - 0.5 - Exxsol D 110 Solvent (s) up to 1 liter - - Solvesso 200 Solvent (s) - up to 1 liter - Witconol 1095 Solvent (s) - - up to 1 liter

The properties of EC preparations were assessed according to the following CIPAC or OECD procedures.

(C) pH value 1% in water (CIPAC MT 75)

The pH of a 1% dilution in demineralized water is determined at 20 ° C using a pH meter and a glass electrode.

(D) Density (OECD guideline 109)

The density of the corresponding EC formulation is measured at 20 ° C using an oscillating densimeter. The characteristics of the EC formulations of Examples 4-6, prepared by the methods described above, are shown in Table II below.

T a b e l a II

Characteristics of EC preparations

Characteristic Research method Example 4 Example 5 Example 6 Characteristics of the emulsion - after 30 min CIPAC MT 36 homogeneous homogeneous homogeneous - after 2 hours homogeneous homogeneous homogeneous - after 24 hours homogeneous homogeneous homogeneous - re-emulsification homogeneous homogeneous homogeneous - stability of the final emulsion homogeneous homogeneous homogeneous Durability CIPAC MT 39 no separate no separate no separate low temperature at 0 ° C substances substances substances pH 1% in water CIPAC MT 75 4.4 not marked not marked Density OECD 109 1.048 g / ml 1.066 g / ml 1.052 g / ml

The foaming capacity of all EC formulations was determined according to the CIPAC MT 47 method. After dilution with water (1-2%) and 30 inversions upside down with a 100 ml measuring cylinder filled with 100 ml water, the persistent foam content was less than 20 ml.

E x g l e s 7-9

EC preparations were produced containing:

Ingredient Function Concentration (g / l) Example 7 8 9 Picolinafen Active substance (s) 50 100 100 2,4-D 2-EH Active substance (b) 422 844 844 Ukanil 2507 Non-ionic surfactant (c) 60 60 60 Rhodacal 60 / BE Anionic surfactant (d) 60 60 60 AgsolEx BLO Solvent (s) up to 1 liter up to 1 liter - AgsolEx1 Solvent (s) - - up to 1 liter

PL 200 931 B1

The characteristics of the EC formulations of Examples 7-9, obtained by the methods described above, are shown in Table III below.

T a b e l a III

Characteristics of EC preparations

Characteristic Research method Example 7 Example 8 Example 9 Characteristics of the emulsion - after 30 minutes - after 2 hours - after 24 hours - re-emulsification - stability of the final emulsion CIPAC MT 36 homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous homogeneous 0.5 ml of oil homogeneous Durability low temperature at 0 ° C CIPAC MT 39 no secreted substance no secreted substance no secreted substance pH 1% in water CIPAC MT 75 6.4 6.2 not marked Density OECD 109 1.133 g / ml 1.141 g / ml not marked

The diluted spray formulations (emulsions) of Examples 7-9 are stable despite the presence of water-miscible substances (N-methylpyrrolidone, γ-butyrolactone). The ingredients have environmentally friendly properties. The foaming capacity of the EC formulations was assessed according to the CIPAC MT 47 method. After dilution with water (1-2%) and 30 inversions upside down with a 100 ml measuring cylinder filled with 100 ml water, the persistent foam content was less than 20 ml.

Claims (8)

A non-aqueous herbicidal formulation in the form of an emulsifiable concentrate containing herbicidally active compounds for plant protection, characterized in that it comprises (a) 25-150 g / liter of at least one fluorinated herbicidal compound of formula I, wherein R ¹ and R ³ independently represent fluoro or fluoroalkyl, ₂ R ² is hydrogen or optionally substituted alkyl or alkoxy; amines independently represent an integer of 1-2; (b) 400 - 900 g / liter of one or more herbicidal alkyl phenoxyalkanoates, (c) 10 - 100 g / liter of at least one nonionic surfactant, (d) 10 - 100 g / liter of at least one benzenesulfonate, (e ) 50-600 g / L of one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, methylated vegetable oils and water-miscible polar aprotic organic solvents, and (f) optionally up to 5 g / L of antifoam. 2. The formulation according to claim 1 The method of claim 1, wherein the fluorinated herbicidal compound (a) is N- (4-fluorophenyl) -2- (3-a, α, α-trifluoromethylphenoxy) -6-pyridinecarboxamide. 3. A formulation according to claim 1 The process of claim 1, wherein the herbicidal alkyl phenoxyalkanoate (b) is an alkyl phenoxyacetate of formula II PL 200 931 B1 in which R ⁴ independently represents halogen or C1-C6 alkyl, R ⁵ and R ⁶ independently represent C 1 -C 6 alkyl, R ⁷ is hydrogen or methyl and t is an integer from 1 to 3. 4. A formulation according to claim 1 A compound as claimed in any one of the preceding claims, wherein the alkyl phenoxyacetate (b) is a compound selected from the group consisting of 2-ethylhexyl (4-chloro-2-methylphenoxy) acetate, 2-ethylhexyl (2,4-dichlorophenoxy) acetate and 2 2-ethylhexyl - (4-chloro-2-methylphenoxy) propionate and mixtures thereof. 5. A formulation according to claim 1 The process of claim 1, wherein the nonionic surfactant (c) is ethoxylated castor oil. 6. A formulation according to claim 1 A process as claimed in claim 1, characterized in that the benzene sulphonate (d) is calcium alkyl benzene sulphonate. 7. A formulation according to claim 1 A method according to claim 1, characterized in that it comprises: (a) 30-125 g / liter of at least one fluorinated herbicidal compound of formula I; (b) 700-875 g / L of one or more herbicidal alkyl phenoxyalkanoates of formula II; (c) 20-75 g / L of at least one nonionic surfactant; (d) 20-75 g / L of at least one sodium or calcium alkylbenzene sulfonate; (e) 50-200 g / L of one or more solvents selected from the group consisting of aliphatic and aromatic hydrocarbons, _{methyl (C 8} -C ₁₂ ) carboxylates, N-methylpyrrolidone, γ-butyrotactone and isopropyl lactate; and (f) optionally up to 2 g / L of at least one antifoam agent selected from the group consisting of polydimethylsiloxanes and perfluoroalkylphosphonic / perfluoroalkylphosphinic acids. A method of controlling undesirable vegetation at the site of occurrence, characterized in that the formulation as defined in claim 1 is emulsified. 1 with water, and the site is treated with the resulting dilute aqueous formulation.